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EP1028102B1 - Procédé pour l'isomérisation d'alklyphénols en présence d'un catalyseur acide solide - Google Patents

Procédé pour l'isomérisation d'alklyphénols en présence d'un catalyseur acide solide Download PDF

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Publication number
EP1028102B1
EP1028102B1 EP00200298A EP00200298A EP1028102B1 EP 1028102 B1 EP1028102 B1 EP 1028102B1 EP 00200298 A EP00200298 A EP 00200298A EP 00200298 A EP00200298 A EP 00200298A EP 1028102 B1 EP1028102 B1 EP 1028102B1
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EP
European Patent Office
Prior art keywords
ipp
isomerization
catalyst
ortho
composition
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP00200298A
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German (de)
English (en)
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EP1028102A1 (fr
Inventor
Anantha Narayan Desikan
George Edward Whitwell
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Akzo Nobel NV
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Akzo Nobel NV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring

Definitions

  • the present invention relates to the isomerization of an alkylation product, formed by the alkylation of phenol with an olefin in the presence of a super acid catalyst containing Br ⁇ nsted acid functionality.
  • isomerization as used herein, is meant to indicate the change in overall isomer distribution of an alkylated phenol composition by intra- and/or intermolecular mechanism(s).
  • Such a product normally contains a certain level of undesired mono, di and trisubstituted ortho-alkylphenols (or mixture thereof).
  • phosphorylation of such materials is a well-known reaction and involves treating them with a phosphorylating reagent (such as phosphorus oxytrichloride) at moderately elevated temperature (such as about 100°C to about 200°C), preferably in the presence of a Friedel-Crafts catalyst.
  • a phosphorylating reagent such as phosphorus oxytrichloride
  • trifluoromethane sulfonic acid catalyst While the use of trifluoromethane sulfonic acid catalyst, as just described, has been utilized commercially, its use is attendant with certain disadvantages.
  • the use of relatively high levels of this catalyst e.g., 800 to 1000 ppm
  • Trifluoromethane sulfonic acid is a strong acid that can cause corrosion damage in the process equipment that is used. This catalyst cannot be recovered and hence the catalyst costs are not trivial.
  • the isomerization reaction using this acid is rather slow (e.g., 40 to 60 hours) in order to reach the target isomer distribution.
  • the present invention relates to the isomerization of an alkylated phenol composition comprising ortho-substituted C 3 - or C 4 -alkyl phenol, which comprises heating said composition in the presence of an effective amount of a solid acid catalyst wherein a composition comprising from about 10% to 20% by weight of mono-ortho-substituted alkylated phenols, from about 5% to about 20% by weight of mono-meta-substituted alkylated phenols, from about 10% to about 30% by weight of mono-para-substituted alkylated phenols, and from about 0.5% to 3% 2,6-di-alkylphenol is formed.
  • the alkylation product which is treated herein will comprise a mixture of alkylated phenols: from about 10% to about 30%, by weight of the mono-ortho-substituted alkylated phenols; from about 0% to about 5%, by weight of mono-meta-substituted alkylated phenols; from about 5% to about 15%, by weight of mono-para-substituted alkylated phenols; from 2% to 10% by weight 2,6-dialkylated phenol; and from 1% to 5% tri-alkylated phenol.
  • the present invention relies upon a solid acid catalyst, as will be described below in further detail, to lower the amount of such mono and di-ortho-substituted species so that the final product has the following composition: from about 10% to about 20%, by weight of mono-ortho-substituted alkylated phenols; from about 5% to about 20%, by weight of mono-meta-substituted alkylated phenols; from about 10% to about 30%, by weight of mono-para-substituted alkylated phenols; and from about 0.5% to 3% 2,6-di-alkylphenol.
  • the present invention is useful, for example, in the isomerization of mono-ortho-alkylsubstituted phenols, such as monoisopropylphenol, of di-orthoalkylsubstituted phenols, such as 2,6-diisopropylphenol, or mixtures containing such alkylated species.
  • the alkyl group or groups on the phenols which are treated has three or four carbon atoms, such as exemplified by the isopropyl and tert-butyl groups. Most preferaby, it is an isopropyl group.
  • the general type of isomerization reaction is shown in the aforementioned Giolito et al. patent in which the catalyst is employed at a level of from about 0.01% to about 5%, by weight of the alkylphenol, preferably from about 300 to 3000 ppm (about 0.03 to 0.3% by weight), and the reaction temperature for the isomerization reaction will be in the range of from about 170°C to the reflux temperature of the alkylphenol-containing composition which is treated preferably from about 100°C to about 250°C.
  • the reaction can be performed advantageously at atmospheric pressure or elevated pressure (e.g., up to about 500 psig (34.4x10 5 Pa)).
  • the present process is practiced in the absence of an alkylating agent, such as an olefin.
  • solid acid catalyst types which are well known to the person of ordinary skill in the art for other chemical reactions, can be used herein. Included as general types of such solid acid catalysts are the H-form zeolites, the supported sulfonic acids, and the heteropoly acids.
  • H-form zeolites which form a well-known class of commercially available materials, which find preferred utility in the present invention are the Y-type zeolites and the beta zeolites. Such materials contain Br ⁇ nsted acid functionality that is needed in the process of the present invention.
  • the ZSM (ex Mobil) type and mordenite class of zeolites also can be used, but they have been found to have somewhat lower activity.
  • the zeolites that are used herein preferably have a silica/alumina ratio of from about 5 to about 100, most preferably from about 5 to about 80.
  • Representative supported sulfur acid catalysts include the sulfonic acid catalysts, sulfated zirconia (commercially available, for example, from MEI Chemicals) and the perfluorinated ionic exchange polymers that are available from DuPont under the trademark NAFION. The latter type of material is described at Col. 2, line 24 to Col. 3, line 47 of U.S. Patent No. 5,001,281 to S.M. Li, which description is incorporated herein by reference.
  • the supported sulfur acid catalyst is a sulfated zirconia catalyst.
  • a supported heteropoly acid catalyst can also be used in connection with the present invention.
  • the Knifton patent deals with the use of such heteropoly acid materials in the synthesis, rather than in the isomerization, of an alkylphenol composition.
  • the present invention's catalyst selection has a number of advantages, as compared to the use of the liquid catalyst trifluoromethane sulfonic acid previously described.
  • the use of a solid catalyst precludes the possibility that it will become lost by dissolution in the liquid reaction media. There is also no need to use the more difficult means needed to separate a liquid catalyst from a liquid reaction product.
  • the solid acid catalyst is more amenable to a continuous reaction process as compared to the use of a liquid catalyst.
  • the solid catalyst used herein is more easy to regenerate than the trifluoromethane sulfonic acid catalyst that has been previously described.
  • the solid acid catalysts that are described for use herein have been found to generally yield a product having lower color characteristics than were achieved in many cases using the trifluoromethane sulfonic acid catalyst of the prior art.
  • compositions comprise a mixture of alkylphenols wherein the ratio of mono-ortho- to mono- meta- and mono-para- isomers is 2 or lower, preferably 1.5 or lower, more preferably 1 or lower, most preferably 0.85 or lower.
  • Such compositions could also be obtained when a sulfated zirconia was used as the catalyst.
  • the use of the latter catalyst has disadvantages over the use of the zeolite catalysts in respect of cost and ease of regenerability.
  • the present process can be practiced using a variety of reaction schemes.
  • zeolite catalyst In those cases where a zeolite catalyst is employed, it has been found that such catalysts undergo varying levels of deactivation, due to the formation of carbonaceous species that block the active sites. Such a catalyst can be easily regenerated using known regeneration procedures. For example, a controlled burnout of the carbonaceous species can be achieved using air/nitrogen mixtures that are lean in oxygen at temperatures of from about 200°C to about 500°C.
  • Isomerization reactions were carried out using catalysts both in a fixed bed reactor and in a stirred batch reactor. Tests using the fixed bed reactor were carried out at the desired temperatures (150-250°C) and pressures (atmospheric to 150 psig (10.3x10 5 Pa)). Catalysts used were powders or crushed particles in a narrow mesh range or commercial extrudates. Alkylated phenol was pumped into the reactor as a liquid and was heated to about 180°C before contacting the catalyst. Nitrogen was used sometimes as an inert carrier gas. The reactants were fed into the top of the catalyst bed.
  • Liquid isomerized phenol was collected in a gas/liquid separator, and the liquid samples were analyzed with a gas chromatograph, using a flame ionization detector. The results reported are in GC area % and can be converted into the wt% by using the appropriate response factors, i.e. 1.07 for phenol, 0.96 for 2-IPP (i.e. o-IPP), 2,6-di-IPP, 2,4-di-IPP, 2,5-di-IPP, and tri-IPP, 1.00 for 4-IPP (i.e. p-IPP), and 0.98 for 3-IPP (i.e. m-IPP) and 3,5-di-IPP (IPP stands for isopropylphenol). Catalysts were pretreated in situ as needed prior to the isomerization reaction.
  • 2-IPP i.e. o-IPP
  • 2,6-di-IPP 2,4-di-IPP
  • 2,5-di-IPP 2,
  • LHSV Liquid Hourly Space Velocity.
  • the ratio o/m+p is calculated from the amount (GC area % or wt%) of o-IPP divided by the amount of m-IPP plus the amount of p-IPP.
  • This Example illustrates the isomerization of an isopropylated phenol composition using a SO 4 /ZrO 2 (sulfated zirconia) catalyst.
  • SO 4 /ZrO 2 extrudates obtained from Magnesium Elektron Limited, was loaded into a stainless steel reactor and was calcined in dry air at 600°C - 650°C for two hours. The catalyst was then brought to 180°C and the system was purged with a N 2 stream prior to the isomerization reaction.
  • Table 1 The results of the isomerization are summarized in Table 1.
  • This Example illustrates the isomerization of an isopropylated phenol composition over a beta zeolite catalyst obtained from Zeolyst International (CBV 861E).
  • CBV 861E Zeolyst International
  • This Example illustrates the isomerization of an isopropylated phenol composition on a perfluorinated ion-exchange polymer (NAFION brand from DuPont) on a silica support.
  • NAFION brand/SiO 2 extrudates about 1.0 g of the NAFION brand/SiO 2 extrudates, was loaded into a stainless steel reactor and dried in a nitrogen gas stream at 150°C for four hours prior to the evaluation. The catalyst was then brought to 155°C while in the nitrogen gas stream. Isomerization was carried out at 55°C and at atmospheric pressure. The results are summarized in Table 3.
  • Zeolite type Y is also effective, as shown herein, at catalyzing the isomerization of ortho-substituted isopropylphenols to more stable meta isomers.
  • HY Zeolite obtained from Zeolyst International (CBV 712 Si/Al ratio 12) was used as 14-30 mesh size particles. The following Table 4 summarizes the results.
  • HY Zeolite (Zeolyst CBV 780 - Si/Al: 80) was used as described in the previous example and also found to be effective for the isomerization reaction.
  • the following Table 6 summarizes the results. Time (h) 2:00 3:00 4:00 6:00 7:00 19:40 23:30 Day 1 1 1 1 1 1 1 1 LHSV (h -1 ) 1 1 1 1 1 1 1 Temp.
  • the HY Zeolite extrudates which are described in Example 8, after about 500 hours on stream were subjected to a rapid deactivation test and were regenerated using air at 450°C for about 4-6 hours.
  • the regenerated catalyst was tested for its isomerization activity, and the results are summarized in Table 9.
  • This Example illustrates the phosphorylation of the isomerized product of the present invention.
  • About 120 g of the isomerized product was phosphorylated with about 150 g of phosphorus oxytrichloride in the presence of 0.5 g of magnesium dichloride at atmospheric pressure and a temperature of about 180°C.
  • the phosphorylated sample was stripped under vacuum to remove free phenolics and was washed with oxalic acid and caustic solutions to remove the catalyst.
  • the product was then dried under vacuum for about four hours to reduce the water level in the product to about 100 ppm.
  • composition of the alkylated phosphate ester was determined to be (in GC area %): phenol: 42.7; o-IPP: 13.6; m+p-IPP: 35.3; 2,6-di-IPP: 0.1; 2,4-di-IPP: 1.4; 2,5- and 3,5-di-IPP: 3.9; 2,3-di-IPP: 0.1; 2,4,6-tri-IPP: 2.6; other tri-IPP: 0.2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (6)

  1. Procédé pour l'isomérisation d'une composition de phénol alkylé comprenant du phénol ortho-substitué par un alkyle en C3 ou C4, qui comprend le chauffage de ladite composition en présence d'une quantité efficace d'un catalyseur acide solide, dans lequel une composition comprenant d'environ 10 % à 20 % en poids de phénols alkylés mono-ortho-substitués, d'environ 5 % à environ 20 % en poids de phénols alkylés mono-méta-substitués, d'environ 10 % à environ 30 % en poids de phénols alkylés mono-para-substitués, et d'environ 0,5 % à 3 % de 2,6-di-alkylphénol est formée.
  2. Procédé selon la revendication 1, caractérisé en ce que le catalyseur acide solide est une zéolite de forme H, un acide de soufre supporté ou un hétéropolyacide supporté.
  3. Procédé selon la revendication 2, caractérisé en ce que la zéolite de forme de H est une zéolite de type Y ou bêta.
  4. Procédé selon la revendication 2, caractérisé en ce que l'acide de soufre supporté est un zircone sulfaté.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le groupe alkyle en C3 ou C4 est un groupe isopropyle ou tert-butyle.
  6. Procédé selon l'une quelconque des revendications précédentes, comprenant de plus la phosphorylation de la composition de phénol alkylé isomérisé.
EP00200298A 1999-02-02 2000-01-27 Procédé pour l'isomérisation d'alklyphénols en présence d'un catalyseur acide solide Expired - Lifetime EP1028102B1 (fr)

Applications Claiming Priority (2)

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US24191199A 1999-02-02 1999-02-02
US241911 1999-02-02

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EP1028102B1 true EP1028102B1 (fr) 2005-05-25

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US (2) US6784325B2 (fr)
EP (1) EP1028102B1 (fr)
JP (1) JP2000226351A (fr)
AT (1) ATE296276T1 (fr)
CA (1) CA2297855A1 (fr)
DE (1) DE60020277T2 (fr)

Families Citing this family (2)

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MXPA02003273A (es) * 2002-04-01 2003-10-06 Mexicano Inst Petrol Composicion olefinica con alto indice de octano que disminuye el nivel de emisiones contaminantes en vehiculos automotores.
US7074737B2 (en) 2003-12-23 2006-07-11 Supresta U.S. Llc Alkylation of triphenylphosphate

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Also Published As

Publication number Publication date
EP1028102A1 (fr) 2000-08-16
US6486339B2 (en) 2002-11-26
DE60020277D1 (de) 2005-06-30
JP2000226351A (ja) 2000-08-15
US20010025126A1 (en) 2001-09-27
CA2297855A1 (fr) 2000-08-02
US6784325B2 (en) 2004-08-31
ATE296276T1 (de) 2005-06-15
US20020040169A1 (en) 2002-04-04
DE60020277T2 (de) 2006-01-26

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